Method for preventing exhaust valve seat recession

ABSTRACT

A method for preventing or inhibiting exhaust valve seat recession in a natural gas fueled internal combustion engine is disclosed. The method involves lubricating the engine with a lubricating oil composition comprising (a) a major amount of an oil of lubricating viscosity, and (b) a minor amount of a natural gas engine oil additive package, wherein the lubricating oil composition is substantially free of each of any zinc compounds and alkaline earth metal salts of a condensation product of an alkylene polyamine, an aldehyde and a substituted phenol.

PRIORITY

This application is a continuation of co-pending U.S. patent application Ser. No. 12/378,678 filed Feb. 18, 2009, the contents of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Technical Field

The present invention generally relates to a method for preventing or inhibiting exhaust valve seat recession in natural gas fueled internal combustion engines.

2. Description of the Related Art

Natural gas fueled engines are engines that use natural gas as a fuel source. Lubricating oils with high resistance to oxidation, nitration and viscosity increase are generally preferred for lubricating oils used in natural gas engines because of the conditions related to this type of engine.

Natural gas has a higher specific heat content than liquid hydrocarbon fuels and therefore it will burn hotter than liquid hydrocarbon fuels under typical conditions. In addition, since it is already a gas, natural gas does not cool the intake air by evaporation as compared to liquid hydrocarbon fuel droplets. Furthermore, many natural gas fueled engines are run either at or near stoichiometric conditions, where less excess air is available to dilute and cool combustion gases. As a result, natural gas fueled engines generate higher combustion gas temperatures than engines burning liquid hydrocarbon fuels. In most cases, natural gas fueled engines are used continuously at 70 to 100% load, whereas an engine operating in vehicular service may only spend 50% of its time at full load.

This condition of running continuously near full load places severe demands on the lubricant. For example, by subjecting the lubricating to a sustained high temperature environment, the life of the lubricant is often limited by oil oxidation processes. Also, since the rate of formation of nitrogen (NOx), increases exponentially with temperature, natural gas fueled engines may generate NO_(x) concentrations high enough to cause severe nitration of lubricating oil.

Good valve wear control is also important for keeping engine operating costs down and may be achieved by providing the proper amount and composition of ash. In addition, minimizing combustion chamber deposits and spark plug fouling are considerations in setting the ash content in these oils. Lubricating oil ash levels are limited, so detergents must be carefully selected to minimize piston deposits and ring sticking.

Valve wear resistance is important to the durability of natural gas fueled engines. In general, exhaust valve recession is wear which occurs at the valve and valve seat interface and is the most pronounced form of valve wear in natural gas fueled engines. When the valve is prevented from seating properly, it can cause engine roughness, poor fuel economy and excessive emissions. In order to correct excessive valve wear, a cylinder head overhaul is usually required. Although natural gas fueled engines typically use very hard corrosion-resistant material for the valve face and seat mating surface to give extended cylinder head life, it does not completely eliminate valve recession.

There is a difference in the lubricating oil requirements for natural gas fueled engines and engines that are fueled by liquid hydrocarbon fuels. The combustion of liquid hydrocarbon fuels such as diesel fuel often results in a small amount of incomplete combustion (e.g., exhaust particulates). In a liquid hydrocarbon fueled engine, these incombustibles provide a small but critical degree of lubrication to the exhaust valve/seat interface, thereby ensuring the durability of both cylinder heads and valves.

Natural gas fueled engines burn fuel that is introduced to the combustion chamber in the gaseous phase. The combustion of natural gas fuel is often very complete, with virtually no incombustible materials. This has a significant affect on the intake and exhaust valves because there is no fuel-derived lubricant such as liquid droplets or soot to aid in lubrication to the exhaust valve/seat interface in a natural gas fueled engine. Therefore, the durability of the cylinder head and valve is controlled by the ash content and other properties of the lubricating oil and its consumption rate to provide lubricant between the hot valve face and its mating seat. Too little ash or the wrong type can accelerate valve and seat wear, while too much ash may lead to valve guttering and subsequent valve torching. Too much ash can also lead to loss of compression or detonation from combustion chamber deposits. Consequently, gas engine builders frequently specify a narrow ash range that they have learned provides the optimum performance. Since most gas is low in sulfur, excess ash is generally not needed to address alkalinity requirements, and ash levels are largely optimized around the needs of the valves. There may be exceptions to this in cases where sour gas or landfill gas is used.

Zinc dialkyldithiophosphates are a very effective additive used in natural gas engine oil additive packages for anti-wear and oxidation protection and, for example, has been shown to contribute to the ash formed on the exhaust valve. However, it is believed that zinc dialkyldithiophosphates may actually chemically react with the surface or form a compound with the other sources of ash that can be easily removed from the valve surface.

In addition, a problem associated with the use of zinc dialkyldithiophosphate is that their phosphorus and sulfur derivatives poison the catalyst components of the catalytic converters. This is a major concern as effective catalytic converters are needed to reduce pollution and to meet governmental regulation designed to reduce toxic gases such as, for example, hydrocarbons, carbon monoxide and nitrogen oxides, in the internal combustion engine exhaust emissions. Such catalytic converters generally use a combination of catalytic metals, e.g., platinum and metal oxides, and are installed in the exhaust streams, e.g., the exhaust pipes of automobiles, to convert the toxic gases to nontoxic gases. Accordingly, it would be desirable to eliminate the amount of zinc dialkyldithiophosphate in lubricating oils, thus reducing catalyst deactivation and hence increasing the life and effectiveness of catalytic converters while also meeting future industry standard proposed phosphorus and sulfur contents in the engine oil. However, simply decreasing the amount of zinc dialkyldithiophosphate presents problems because this necessarily lowers the antiwear properties and oxidation inhibition properties of the lubricating oil. Therefore, it is necessary to find a way to retain the antiwear and oxidation properties of the engine oils.

U.S. Pat. No. 3,798,163 (“the '163 patent”) discloses a method for controlling or inhibiting exhaust valve recession in natural gas fueled internal combustion engines by maintaining a lubricating amount of a lubricating oil composition on the engine components of the internal combustion engine. The '163 patent further discloses that the lubricating oil composition contains (a) a major amount of an oil of lubricating viscosity, (b) at least one alkaline earth metal sulfonate in an amount sufficient to improve the detergency of the composition, and (c) at least one alkaline earth metal salt of a condensation product of (i) an alkylene polyamine, (ii) an aldehyde, and (iii) a substituted phenol, wherein the alkaline earth metal salt of the condensation product is present in an amount sufficient to inhibit the recession of the engine's exhaust valves into the engine cylinder head.

U.S. Pat. No. 5,726,133 (“the '133 patent”) discloses a low ash gas engine oil comprising a major amount of a base oil of lubricating viscosity and a minor amount sufficient to contribute a sulfated ash content of about 0.1 to 0.6% ash by ASTM D 874 of an additive mixture comprising a mixture of detergents comprising at least one first alkali or alkaline earth metal salt or mixture thereof of low Total Base Number (TBN) of about 250 and less and at least one second alkali or alkaline earth metal salt or mixture thereof which is more neutral than the first low TBN salt. The '133 patent further discloses that the fully formulated gas engine oil can also typically contain other standard additives known to those skilled in the art, including antiwear additives such as zinc dithiophosphates, dispersants, phenolic or aminic antioxidants, metal deactivators, pour point depressants, antifoaming agents, and viscosity index improvers.

U.S. Pat. No. 6,174,842 (“the '842 patent”) discloses a lubricating composition containing (a) a major amount of lubricating oil, (b) an oil-soluble molybdenum compound substantially free of reactive sulfur, (c) an oil-soluble diarylamine and (d) an alkaline earth metal phenate. The '842 patent further discloses that the composition can further include a zinc dihydrocarbyl dithiophosphate as an antiwear agent. In addition, Oil Blend 18 disclosed in Example 2 of the '842 patent contained an antiwear agent and was evaluated for exhaust valve recession in a Cummins Natural Gas Engine test.

It is desirable to develop improved methods for preventing or inhibiting exhaust valve recession in natural gas fueled internal combustion engines employing a lubricating oil composition free of at least any zinc compound and which utilizes a minimum number of components.

SUMMARY OF THE INVENTION

In accordance with one embodiment of the present invention, there is provided a method for preventing or inhibiting exhaust valve seat recession in a natural gas fueled engine, the method comprising lubricating the engine with a lubricating oil composition comprising (a) a major amount of an oil of lubricating viscosity, and (b) a minor amount of a natural gas engine oil additive package, wherein the lubricating oil composition is substantially free of each of any zinc compounds and alkaline earth metal salts of a condensation product of an alkylene polyamine, an aldehyde and a substituted phenol.

In accordance with a second embodiment of the present invention, there is provided a method for enhancing the life of an exhaust valve in a natural gas fueled engine as evidenced by protection or inhibition in exhaust valve seat recession in the natural gas fueled engine, the method comprising lubricating the engine with a lubricating oil composition comprising (a) a major amount of an oil of lubricating viscosity, and (b) a minor amount of a natural gas engine oil additive package, wherein the lubricating oil composition is substantially free of each of any zinc compounds and alkaline earth metal salts of a condensation product of an alkylene polyamine, an aldehyde and a substituted phenol.

In accordance with a third embodiment of the present invention, the use of a lubricating oil composition comprising (a) a major amount of an oil of lubricating viscosity, and (b) a minor amount of a natural gas engine oil additive package, wherein the lubricating oil composition is substantially free of each of any zinc compounds and alkaline earth metal salts of a condensation product of an alkylene polyamine, an aldehyde and a substituted phenol for the purpose of preventing or inhibiting exhaust valve seat recession in a natural gas fueled engine is provided.

In accordance with a fourth embodiment of the present invention, a natural gas engine lubricating oil composition is provided comprising (a) a major amount of an oil of lubricating viscosity, (b) one or more ashless dispersants, (c) one or more metal-containing detergents, and (d) one or more antioxidants, wherein the lubricating oil composition is substantially free of each of any zinc compounds and alkaline earth metal salts of a condensation product of an alkylene polyamine, an aldehyde and a substituted phenol.

In accordance with a fifth embodiment of the present invention, a natural gas engine lubricating oil composition is provided comprising (a) a major amount of an oil of lubricating viscosity, (b) one or more ashless dispersants, (c) one or more metal-containing detergents, and (d) one or more antioxidants, wherein the lubricating oil composition is substantially free of each of any zinc compounds and alkaline earth metal salts of a condensation product of an alkylene polyamine, an aldehyde and a substituted phenol, and further wherein the lubricating oil composition has an exhaust valve seat recession reducing property greater than that of a corresponding lubricating oil composition in which a zinc compound is present therein.

In accordance with a sixth embodiment of the present invention, a natural gas engine lubricating oil composition is provided consisting essentially of (a) a major amount of an oil of lubricating viscosity, (b) one or more ashless dispersants, (c) one or more metal-containing detergents, and (d) one or more antioxidants, wherein the lubricating oil composition is substantially free of any zinc compounds.

In accordance with a seventh embodiment of the present invention, there is provided a natural gas fueled internal combustion engine lubricated with a lubricating oil composition comprising (a) a major amount of an oil of lubricating viscosity, and (b) a minor amount of a natural gas engine oil additive package, wherein the lubricating oil composition is substantially free of each of any zinc compounds and alkaline earth metal salts of a condensation product of an alkylene polyamine, an aldehyde and a substituted phenol.

By lubricating a natural gas fueled internal combustion engine with a lubricating oil composition comprising (a) a major amount of an oil of lubricating viscosity, and (b) a minor amount of a natural gas engine oil additive package, wherein the lubricating oil composition is substantially free of each of any zinc compounds and alkaline earth metal salts of a condensation product of an alkylene polyamine, an aldehyde and a substituted phenol, exhaust valve seat recession in the natural gas fueled engine is advantageously prevented or inhibited as compared to a corresponding lubricating oil composition in which a zinc compound such as a zinc dihydrocarbyl dithiophosphate compound is present therein. This is unexpected as zinc dihydrocarbyl dithiophosphate is a known antiwear agent which contributes to the ash formed on the exhaust valve and typically used in a natural gas engine lubricating oil composition.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention is directed to methods for preventing or inhibiting exhaust valve seat recession in a natural gas fueled engine. Generally, the methods involve lubricating a natural gas fueled engine with a lubricating oil composition containing at least (a) a major amount of an oil of lubricating viscosity, and (b) a minor amount of a natural gas engine oil additive package, wherein the lubricating oil composition is substantially free of each of any zinc compounds and alkaline earth metal salts of a condensation product of an alkylene polyamine, an aldehyde and a substituted phenol. The term “substantially free” as used herein shall be understood to mean only trace amounts, typically below 0.001 wt. %, based on the total weight of the lubricating oil composition, if any, of each of the zinc compounds and alkaline earth metal salts of the condensation product in the lubricating oil compositions.

The lubricating oil compositions according to the present invention for use in natural gas fueled engines will have a sulfated ash content of no more than about 1.5 wt. % as determined by ASTM D 874, preferably a sulfated ash content of no more than about 0.95 wt. % as determined by ASTM D 874 and most preferably a sulfated ash content of no more than about 0.5 wt. % as determined by ASTM D 874. In one embodiment, a lubricating oil composition according to the present invention for use in natural gas fueled engines has a sulfated ash content of about 0.1 wt. % to about 1.5 wt. % as determined by ASTM D 874, preferably about 0.12 wt. % to about 0.95 wt. % as determined by ASTM D 874 and most preferably about 0.15 wt. % to about 0.5 wt. % as determined by ASTM D 874. The lubricant ash advantageously acts as a solid lubricant to protect the valve/seat interface in place of naturally occurring exhaust particles in a hydrocarbon fueled engine.

In one embodiment, the lubricating oil composition of the present invention is substantially free of any phosphorus, e.g., a phosphorus content not exceeding 0.08 wt. % and more preferably not exceeding 0.05 wt. %. In another embodiment, the lubricating oil composition of the present invention contains relatively low levels of sulfur, i.e., not exceeding 0.7 wt. %, preferably not exceeding 0.5 wt. % and more preferably not exceeding 0.3 wt. %.

The internal combustion engines to which the present invention is applicable may be characterized as those operated on, i.e., fueled by, natural gas and include internal combustion engines. Examples of such engines include four cycle engines and the like. In a preferred embodiment, the internal combustion engine is a stationary engine used in, for example, well-head gas gathering, compression, and other gas pipeline services; electrical power generation (including co-generation); and irrigation.

The oil of lubricating viscosity for use in the lubricating oil compositions of this invention, also referred to as a base oil, is typically present in a major amount, e.g., an amount of greater than 50 wt. %, preferably greater than about 70 wt. %, more preferably from about 80 to about 99.5 wt. % and most preferably from about 85 to about 98 wt. %, based on the total weight of the composition. The expression “base oil” as used herein shall be understood to mean a base stock or blend of base stocks which is a lubricant component that is produced by a single manufacturer to the same specifications (independent of feed source or manufacturer's location); that meets the same manufacturer's specification; and that is identified by a unique formula, product identification number, or both. The base oil for use herein can be any presently known or later-discovered oil of lubricating viscosity used in formulating lubricating oil compositions for any and all such applications, e.g., engine oils, marine cylinder oils, functional fluids such as hydraulic oils, gear oils, transmission fluids, etc. Additionally, the base oils for use herein can optionally contain viscosity index improvers, e.g., polymeric alkylmethacrylates; olefinic copolymers, e.g., an ethylene-propylene copolymer or a styrene-butadiene copolymer; and the like and mixtures thereof.

As one skilled in the art would readily appreciate, the viscosity of the base oil is dependent upon the application. Accordingly, the viscosity of a base oil for use herein will ordinarily range from about 2 to about 2000 centistokes (cSt) at 100° Centigrade (C). Generally, individually the base oils used as engine oils will have a kinematic viscosity range at 100° C. of about 2 cSt to about 30 cSt, preferably about 3 cSt to about 16 cSt, and most preferably about 4 cSt to about 12 cSt and will be selected or blended depending on the desired end use and the additives in the finished oil to give the desired grade of engine oil, e.g., a lubricating oil composition having an SAE Viscosity Grade of 0W, 0W-20, 0W-30, 0W-40, 0W-50, 0W-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30, 10W-40, 10W-50, 15W, 15W-20, 15W-30, 15W-40, 30, 40 and the like.

Base stocks may be manufactured using a variety of different processes including, but not limited to, distillation, solvent refining, hydrogen processing, oligomerization, esterification, and rerefining. Rerefined stock shall be substantially free from materials introduced through manufacturing, contamination, or previous use. The base oil of the lubricating oil compositions of this invention may be any natural or synthetic lubricating base oil. Suitable hydrocarbon synthetic oils include, but are not limited to, oils prepared from the polymerization of ethylene or from the polymerization of 1-olefins to provide polymers such as polyalphaolefin or PAO oils, or from hydrocarbon synthesis procedures using carbon monoxide and hydrogen gases such as in a Fischer-Tropsch process. For example, a suitable base oil is one that comprises little, if any, heavy fraction; e.g., little, if any, lube oil fraction of viscosity 20 cSt or higher at 100° C.

The base oil may be derived from natural lubricating oils, synthetic lubricating oils or mixtures thereof. Suitable base oil includes base stocks obtained by isomerization of synthetic wax and slack wax, as well as hydrocracked base stocks produced by hydrocracking (rather than solvent extracting) the aromatic and polar components of the crude. Suitable base oils include those in all API categories I, II, III, IV and V as defined in API Publication 1509, 14th Edition, Addendum I, December 1998. Group IV base oils are polyalphaolefins (PAO). Group V base oils include all other base oils not included in Group I, II, III, or IV. Although Group II, III and IV base oils are preferred for use in this invention, these base oils may be prepared by combining one or more of Group I, II, III, IV and V base stocks or base oils.

Useful natural oils include mineral lubricating oils such as, for example, liquid petroleum oils, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types, oils derived from coal or shale, animal oils, vegetable oils (e.g., rapeseed oils, castor oils and lard oil), and the like.

Useful synthetic lubricating oils include, but are not limited to, hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins, e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes), and the like and mixtures thereof; alkylbenzenes such as dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)-benzenes, and the like; polyphenyls such as biphenyls, terphenyls, alkylated polyphenyls, and the like; alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivative, analogs and homologs thereof and the like.

Other useful synthetic lubricating oils include, but are not limited to, oils made by polymerizing olefins of less than 5 carbon atoms such as ethylene, propylene, butylenes, isobutene, pentene, and mixtures thereof. Methods of preparing such polymer oils are well known to those skilled in the art.

Additional useful synthetic hydrocarbon oils include liquid polymers of alpha olefins having the proper viscosity. Especially useful synthetic hydrocarbon oils are the hydrogenated liquid oligomers of C₆ to C₁₂ alpha olefins such as, for example, 1-decene trimer.

Another class of useful synthetic lubricating oils include, but are not limited to, alkylene oxide polymers, i.e., homopolymers, interpolymers, and derivatives thereof where the terminal hydroxyl groups have been modified by, for example, esterification or etherification. These oils are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and phenyl ethers of these polyoxyalkylene polymers (e.g., methyl poly propylene glycol ether having an average molecular weight of 1,000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1,000-1,500, etc.) or mono- and polycarboxylic esters thereof such as, for example, the acetic esters, mixed C₃-C₈ fatty acid esters, or the C₁₃ oxo acid diester of tetraethylene glycol.

Yet another class of useful synthetic lubricating oils include, but are not limited to, the esters of dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acids, alkyl malonic acids, alkenyl malonic acids, etc., with a variety of alcohols, e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc. Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid and the like.

Esters useful as synthetic oils also include, but are not limited to, those made from carboxylic acids having from about 5 to about 12 carbon atoms with alcohols, e.g., methanol, ethanol, etc., polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, and the like.

Silicon-based oils such as, for example, polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxy-siloxane oils and silicate oils, comprise another useful class of synthetic lubricating oils. Specific examples of these include, but are not limited to, tetraethyl silicate, tetra-isopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-hexyl)silicate, tetra-(p-tert-butylphenyl)silicate, hexyl-(4-methyl-2-pentoxy)disiloxane, poly(methyl)siloxanes, poly(methylphenyl)siloxanes, and the like. Still yet other useful synthetic lubricating oils include, but are not limited to, liquid esters of phosphorous containing acids, e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decane phosphionic acid, etc., polymeric tetrahydrofurans and the like.

The lubricating oil may be derived from unrefined, refined and rerefined oils, either natural, synthetic or mixtures of two or more of any of these of the type disclosed hereinabove. Unrefined oils are those obtained directly from a natural or synthetic source (e.g., coal, shale, or tar sands bitumen) without further purification or treatment. Examples of unrefined oils include, but are not limited to, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from distillation or an ester oil obtained directly from an esterification process, each of which is then used without further treatment. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. These purification techniques are known to those of skill in the art and include, for example, solvent extractions, secondary distillation, acid or base extraction, filtration, percolation, hydrotreating, dewaxing, etc. Rerefined oils are obtained by treating used oils in processes similar to those used to obtain refined oils. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.

Lubricating oil base stocks derived from the hydroisomerization of wax may also be used, either alone or in combination with the aforesaid natural and/or synthetic base stocks. Such wax isomerate oil is produced by the hydroisomerization of natural or synthetic waxes or mixtures thereof over a hydroisomerization catalyst.

Natural waxes are typically the slack waxes recovered by the solvent dewaxing of mineral oils; synthetic waxes are typically the wax produced by the Fischer-Tropsch process. Examples of useful oils of lubricating viscosity include HVI and XHVI basestocks, such isomerized wax base oils and UCBO (Unconventional Base Oils) base oils.

The lubricating oil compositions for use in the method of the present invention will also contain a minor amount of a natural gas engine oil additive package. Typically, an additive package will contain one or more additive components, optionally with one or more diluent oils to make them easy to handle during shipping and storage. Suitable diluents for the additive package include any inert diluent, preferably an oil of lubricating viscosity, so that the additive package may be readily mixed with lubricating oils to prepare lubricating oil compositions. Suitable lubricating oils that may be used as diluents can have a viscosity in the range from about 35 to about 500 Saybolt Universal Seconds (SUS) at 100° F. (38° C.), although any oil of lubricating viscosity may be used. If present, the one or more diluent oils will be present in an amount of about 10 wt. % to about 90 wt. %, based on the total weight of the additive package. The additive package advantageously provides excellent prevention or inhibition of exhaust valve seat recession in a natural gas fueled engine when incorporated into a lubricating oil composition.

Generally, the additive package is present in the lubricating oil composition from about 5 wt. % to about 15 wt. %, and preferably from about 6 wt. % to about 9 wt. %, based on the total weight of the lubricating oil composition. In one embodiment, the additive package contains at least (i) one or more ashless dispersants, (ii) one or more metal-containing detergents, and (iii) one or more antioxidants, wherein the lubricating oil composition is substantially free of each of any zinc compounds, e.g., zinc dialkyl dithiophosphate compound, and alkaline earth metal salts of a condensation product of an alkylene polyamine, an aldehyde and a substituted phenol.

The one or more ashless dispersant compounds employed in the lubricating oil composition of the present invention are generally used to maintain in suspension insoluble materials resulting from oxidation during use, thus preventing sludge flocculation and precipitation or deposition on metal parts. Nitrogen-containing ashless (metal-free) dispersants are basic, and contribute to the base number or BN (as can be measured by ASTM D 2896) of a lubricating oil composition to which they are added, without introducing additional sulfated ash. The term “Base Number” or “BN” as used herein refers to the amount of base equivalent to milligrams of KOH in one gram of sample. Thus, higher BN numbers reflect more alkaline products, and therefore a greater alkalinity. BN was determined using ASTM D 2896 test. An ashless dispersant generally comprises an oil soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed. Many types of ashless dispersants are known in the art.

Representative examples of ashless dispersants include, but are not limited to, amines, alcohols, amides, or ester polar moieties attached to the polymer backbones via bridging groups. An ashless dispersant of the present invention may be, for example, selected from oil soluble salts, esters, amino-esters, amides, imides, and oxazolines of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides; thiocarboxylate derivatives of long chain hydrocarbons, long chain aliphatic hydrocarbons having a polyamine attached directly thereto, and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine.

Carboxylic dispersants are reaction products of carboxylic acylating agents (acids, anhydrides, esters, etc.) comprising at least about 34 and preferably at least about 54 carbon atoms with nitrogen containing compounds (such as amines), organic hydroxy compounds (such as aliphatic compounds including monohydric and polyhydric alcohols, or aromatic compounds including phenols and naphthols), and/or basic inorganic materials. These reaction products include imides, amides, and esters.

Succinimide dispersants are a type of carboxylic dispersant. They are produced by reacting hydrocarbyl-substituted succinic acylating agent with organic hydroxy compounds, or with amines comprising at least one hydrogen atom attached to a nitrogen atom, or with a mixture of the hydroxy compounds and amines. The term “succinic acylating agent” refers to a hydrocarbon-substituted succinic acid or a succinic acid-producing compound, the latter encompasses the acid itself. Such materials typically include hydrocarbyl-substituted succinic acids, anhydrides, esters (including half esters) and halides.

Succinic-based dispersants have a wide variety of chemical structures. One class of succinic-based dispersants may be represented by the formula:

wherein each R¹ is independently a hydrocarbyl group, such as a polyolefin-derived group. Typically the hydrocarbyl group is an alkyl group, such as a polyisobutyl group. Alternatively expressed, the R¹ groups can contain about 40 to about 500 carbon atoms, and these atoms may be present in aliphatic forms. R² is an alkylene group, commonly an ethylene (C₂H₄) group. Examples of succinimide dispersants include those described in, for example, U.S. Pat. Nos. 3,172,892, 4,234,435 and 6,165,235.

The polyalkenes from which the substituent groups are derived are typically homopolymers and interpolymers of polymerizable olefin monomers of 2 to about 16 carbon atoms, and usually 2 to 6 carbon atoms. The amines which are reacted with the succinic acylating agents to form the carboxylic dispersant composition can be monoamines or polyamines.

Succinimide dispersants are referred to as such since they normally contain nitrogen largely in the form of imide functionality, although the amide functionality may be in the form of amine salts, amides, imidazolines as well as mixtures thereof. To prepare a succinimide dispersant, one or more succinic acid-producing compounds and one or more amines are heated and typically water is removed, optionally in the presence of a substantially inert organic liquid solvent/diluent. The reaction temperature can range from about 80° C. up to the decomposition temperature of the mixture or the product, which typically falls between about 100° C. to about 300° C. Additional details and examples of procedures for preparing the succinimide dispersants of the present invention include those described in, for example, U.S. Pat. Nos. 3,172,892, 3,219,666, 3,272,746, 4,234,435, 6,165,235 and 6,440,905.

Suitable ashless dispersants may also include amine dispersants, which are reaction products of relatively high molecular weight aliphatic halides and amines, preferably polyalkylene polyamines. Examples of such amine dispersants include those described in, for example, U.S. Pat. Nos. 3,275,554, 3,438,757, 3,454,555 and 3,565,804.

Suitable ashless dispersants may further include “Mannich dispersants,” which are reaction products of alkyl phenols in which the alkyl group contains at least about 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines). Examples of such dispersants include those described in, for example, U.S. Pat. Nos. 3,036,003, 3,586,629, 3,591,598 and 3,980,569.

Suitable ashless dispersants may also be post-treated ashless dispersants such as post-treated succinimides, e.g., post-treatment processes involving borate or ethylene carbonate as disclosed in, for example, U.S. Pat. Nos. 4,612,132 and 4,746,446; and the like as well as other post-treatment processes. The carbonate-treated alkenyl succinimide is a polybutene succinimide derived from polybutenes having a molecular weight of about 450 to about 3000, preferably from about 900 to about 2500, more preferably from about 1300 to about 2400, and most preferably from about 2000 to about 2400, as well as mixtures of these molecular weights. Preferably, it is prepared by reacting, under reactive conditions, a mixture of a polybutene succinic acid derivative, an unsaturated acidic reagent copolymer of an unsaturated acidic reagent and an olefin, and a polyamine, such as disclosed in U.S. Pat. No. 5,716,912, the contents of which are incorporated herein by reference.

Suitable ashless dispersants may also be polymeric, which are interpolymers of oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substitutes. Examples of polymeric dispersants include those described in, for example, U.S. Pat. Nos. 3,329,658; 3,449,250 and 3,666,730.

In a preferred embodiment of the present invention, an ashless dispersant for use in the lubricating oil composition is a bis-succinimide derived from a polyisobutenyl group having a number average molecular weight of about 700 to about 2300. The dispersant(s) for use in the lubricating oil compositions of the present invention are preferably non-polymeric (e g., are mono- or bis-succinimides).

Generally, the one or more ashless dispersants are present in the lubricating oil composition in an amount ranging from about 1 to about 8 wt. %, and preferably from about 1.5 to about 6 wt. %, based on the total weight of the lubricating oil composition.

The one or more metal-containing detergent compounds employed in the lubricating oil composition of the present invention functions both as a detergent to reduce or remove deposits and as an acid neutralizer or rust inhibitor, thereby reducing wear and corrosion and extending engine life. Detergents generally comprise a polar head with long hydrophobic tail, with the polar head comprising a metal salt of an acid organic compound.

The lubricating oil composition according to the present invention may contain one or more detergents, which are normally salts, and especially overbased salts. Overbased salts, or overbased materials, are single phase, homogeneous Newtonian systems characterized by a metal content in excess of that which would be present according to the stoichiometry of the metal and the particular acidic organic compound reacted with the metal. The overbased materials are prepared by reacting an acidic material (typically an inorganic acid or lower carboxylic acid such as carbon dioxide) with a mixture comprising an acidic organic compound, in a reaction medium comprising at least one inert, organic solvent (such as mineral oil, naphtha, toluene, xylene) in the presence of a stoichiometric excess of a metal base and a promoter.

Useful acidic organic compounds for making the overbased compositions include carboxylic acids, sulfonic acids, phosphorus-containing acids, phenols and mixtures thereof. Preferably, the acidic organic compounds are carboxylic acids or sulfonic acids and hydrocarbyl-substituted salicylic acids.

Carboxylate detergents, e.g., salicylates, can be prepared by reacting an aromatic carboxylic acid with an appropriate metal compound such as an oxide or hydroxide. Neutral or overbased products may then be obtained by methods well known in the art. The aromatic moiety of the aromatic carboxylic acid can contain one or more heteroatoms such as nitrogen and oxygen. Preferably, the moiety contains only carbon atoms. More preferably, the moiety contains six or more carbon atoms, such as a benzene moiety. The aromatic carboxylic acid may contain one or more aromatic moieties, such as one or more benzene rings, optionally fused together or otherwise connected via alkylene bridges. Representative examples of aromatic carboxylic acids include salicylic acids and sulfurized derivatives thereof such as hydrocarbyl substituted salicylic acid and derivatives thereof. Processes for sulfurizing, for example, a hydrocarbyl-substituted salicylic acid, are known to those skilled in the art. Salicylic acids are typically prepared by carboxylation, for example, by the Kolbe-Schmitt process, of phenoxides. In that case, salicylic acids are generally obtained in a diluent in admixture with an uncarboxylated phenol.

Metal salts of phenols and sulfurized phenols are prepared by reaction with an appropriate metal compound such as an oxide or hydroxide. Neutral or overbased products may be obtained by methods well known in the art. For example, sulfurized phenols may be prepared by reacting a phenol with sulfur or a sulfur-containing compound such as hydrogen sulfide, sulfur monohalide or sulfur dihalide, to form products that are mixtures of compounds in which 2 or more phenols are bridged by sulfur-containing bridges.

The metal compounds useful in making the overbased salts are generally any Group I or Group II metal compounds in the Periodic Table of the Elements. Preferably, the metal compounds are Group II metals and include Group IIa alkaline earth metals (e.g., magnesium, calcium, strontium, barium) as well as Group IIb metals such as zinc or cadmium. Preferably, the Group II metals are magnesium, calcium, barium, or zinc, more preferably magnesium or calcium, and most preferably calcium.

Examples of the overbased detergents include, but are not limited to, calcium sulfonates, calcium phenates, calcium salicylates, calcium stearates and mixtures thereof. Overbased detergents suitable for use in the lubricating oil compositions of the present invention may be low overbased, e.g., an overbased detergent having a BN below about 100. The BN of such a low-overbased detergent may be from about 5 to about 50, or from about 10 to about 30, or from about 15 to about 20. Alternatively, the overbased detergents suitable for use in the lubricating oil compositions of the present invention may be high overbased (e.g., an overbased detergent having a BN above about 100). The BN of such a high-overbased detergent may be from about 100 to about 450, or from about 200 to about 350, or from about 250 to about 280. A low-overbased calcium sulfonate detergent with a BN of about 17 and a high-overbased sulfurized calcium phenate with a BN of about 120 are two exemplary overbased detergents for use in the lubricating oil compositions of the present invention.

The lubricating oil compositions according to the present invention may contain more than one overbased detergent, which may be all low-BN detergents, all high-BN detergents, or a mixture thereof. For example, the lubricating oil compositions of the present invention may contain a first metal-containing detergent which is an overbased alkaline earth metal sulfonate or phenate detergent having a BN of about 100 to about 450 and a second metal-containing detergent which is an overbased alkaline earth metal sulfonate or phenate detergent having a BN of about 10 to about 50.

Suitable detergents for use in the lubricating oil compositions also include “hybrid” detergents such as, for example, phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, sulfonates/phenates/salicylates, and the like. Examples of hybrid detergents include those described in, for example, U.S. Pat. Nos. 6,153,565, 6,281,179, 6,429,178, and 6,429,179.

Generally, the one or more metal-containing detergents are present in the lubricating oil composition in an amount ranging from about 0.5 to about 8.5 wt. %, and preferably from about 1 to about 6 wt. %, based on the total weight of the lubricating oil composition. Where two metal-containing detergents are employed, the first metal-containing detergent is present in the lubricating oil composition in an amount ranging from about 0.5 to about 5 wt. %, and preferably from about 1 to about 3 wt. %, and the second metal-containing detergent is present in the lubricating oil composition in an amount ranging from about 0.1 to about 1.0 wt. %, and preferably from about 0.2 to about 0.5 wt. %, based on the total weight of the lubricating oil composition.

The one or more antioxidant compounds employed in the lubricating oil composition of the present invention reduce the tendency of base stocks to deteriorate in service, which deterioration can be evidenced by the products of oxidation such as sludge and varnish-like deposits on the metal surfaces and by viscosity growth. Such oxidation inhibitors include hindered phenols, ashless oil soluble phenates and sulfurized phenates, diphenylamines, alkyl-substituted phenyl and naphthylamines and the like and mixtures thereof. Diphenyamine-type oxidation inhibitors include, but are not limited to, alkylated diphenylamine, phenyl-α-naphthylamine, and alkylated-α-naphthylmine.

Generally, the one or more antioxidant compounds are present in the lubricating oil composition in an amount ranging from about 0.1 to about 3 wt. %, and preferably from about 0.2 to about 2.5 wt. %, based on the total weight of the lubricating oil composition.

The lubricating oil compositions of the present invention can be conveniently prepared by simply blending or mixing the additive package, optionally with other additives, with the oil of lubricating viscosity. The additive package may also be preblended as a concentrate in the appropriate ratios to facilitate blending of a lubricating composition containing the desired concentration of additives. The additive package is blended with the base oil using a concentration at which they are both soluble in the oil and compatible with other additives in the desired finished lubricating oil. Compatibility in this instance generally means that the present compounds as well as being oil soluble in the applicable treat rate also do not cause other additives to precipitate under normal conditions. Suitable oil solubility/compatibility ranges for a given compound of lubricating oil formulation can be determined by those having ordinary skill in the art using routine solubility testing procedures. For example, precipitation from a formulated lubricating oil composition at ambient conditions (about 20° C. to 25° C.) can be measured by either actual precipitation from the oil composition or the formulation of a “cloudy” solution which evidences formation of insoluble wax particles.

As previously stated, the lubricating oil compositions described herein are substantially free of any zinc compounds and alkaline earth metal salts of a condensation product of an alkylene polyamine, an aldehyde and a substituted phenol. In one embodiment, the lubricating oil compositions are also substantially free of any molybdenum-containing compounds. The alkylene polyamines of the condensation product can the following structure NH₂[R(R)—NH]_(n)H wherein R is an alkylene radical containing from about 2 about 6 carbon atoms, and n is an integer from 1 to about 10. Typical alkylene polyamines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine and the like. The aldehydes are generally aliphatic aldehydes which contain from one to about 3 carbon atoms per molecule. The substituted phenols are the alkylated monohydric phenols having at least one alkyl group of sufficient length to impart oil-solubility to the condensation products. Representative alkyl phenols are those in which the alkyl group contains from about 4 to about 24 carbon atoms, and preferably those having from about 8 to about 24 carbon atoms, such as, for example, n-amyl phenol, diamylphenol, octyl phenol, nonyl phenol, p-ter-octyl phenol, a mixture of phenols, wax alkylated phenols and the like.

The lubricating oil compositions for use in the method of the present invention may also contain other conventional additives for imparting auxiliary functions to give a finished lubricating oil composition in which these additives are dispersed or dissolved. For example, the lubricating oil compositions may be blended with antiwear agents other than zinc-containing antiwear agents such as zinc dialkyl dithiophosphate, rust inhibitors, dehazing agents, demulsifying agents, metal deactivating agents, friction modifiers, pour point depressants, antifoaming agents, co-solvents, package compatibilisers, corrosion-inhibitors, dyes, extreme pressure agents and the like and mixtures thereof. A variety of the additives are known and commercially available. These additives, or their analogous compounds, can be employed for the preparation of the lubricating oil compositions of the invention by the usual blending procedures.

Examples of rust inhibitors include, but are not limited to, nonionic polyoxyalkylene agents, e.g., polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol monooleate, and polyethylene glycol monooleate; stearic acid and other fatty acids; dicarboxylic acids; metal soaps; fatty acid amine salts; metal salts of heavy sulfonic acid; partial carboxylic acid ester of polyhydric alcohol; phosphoric esters; (short-chain) alkenyl succinic acids; partial esters thereof and nitrogen-containing derivatives thereof; synthetic alkarylsulfonates, e.g., metal dinonylnaphthalene sulfonates; and the like and mixtures thereof.

Examples of friction modifiers include, but are not limited to, alkoxylated fatty amines; borated fatty epoxides; fatty phosphites, fatty epoxides, fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids, fatty acid amides, glycerol esters, borated glycerol esters; and fatty imidazolines as disclosed in U.S. Pat. No. 6,372,696, the contents of which are incorporated by reference herein; friction modifiers obtained from a reaction product of a C₄ to C₇₅, preferably a C₆ to C₂₄, and most preferably a C₆ to C₂₀, fatty acid ester and a nitrogen-containing compound selected from the group consisting of ammonia, and an alkanolamine and the like and mixtures thereof.

Examples of antifoaming agents include, but are not limited to, polymers of alkyl methacrylate; polymers of dimethylsilicone and the like and mixtures thereof.

Each of the foregoing additives, when used, is used at a functionally effective amount to impart the desired properties to the lubricant. Thus, for example, if an additive is a friction modifier, a functionally effective amount of this friction modifier would be an amount sufficient to impart the desired friction modifying characteristics to the lubricant. Generally, the concentration of each of these additives, when used, ranges from about 0.001% to about 20% by weight, and in one embodiment about 0.01% to about 10% by weight based on the total weight of the lubricating oil composition.

The following non-limiting examples are illustrative of the present invention.

Example 1

A lubricating oil composition was formed containing 3.3 wt. % of a bis-succinimide (derived from a 1300 MW polyisobutenyl succinic anhydride (PIBSA)) and a mixture of heavy polyamine and diethylenetriamine, 0.43 wt. % of a calcium sulfonate (17 BN), 3.0 wt. % of a sulfurized calcium phenate (114 BN), 0.9 wt. % of a hindered phenol antioxidant, 5 ppm of a foam inhibitor and the balance being a Group II base oil. The lubricating oil composition had a sulfated ash content of 0.46 wt. % as determined by ASTM D 874.

Comparative Example A

A lubricating oil composition was prepared by top-treating the lubricating oil composition of Example 1 with 0.38 wt. % of a zinc dialkyldithiophosphate derived from a primary alcohol. The lubricating oil composition had a sulfated ash content of 0.50 wt. % as determined by ASTM D 874.

Testing

The lubricating oil compositions of Example 1 and Comparative Example A were evaluated for exhaust valve seat recession prevention efficacy in a Waukesha F11 GSID engine. In this test, a 6-cylinder 250 BHP Waukesha F11 GSID engine was instrumented in order to obtain dynamic voltage measurements (e.g., as described in U.S. Pat. No. 4,672,843) from the 12 valves—6 intake and 6 exhaust valves. Each test was run for 400 hours at 1800 rpm operated at 90% load. Stoichiometric conditions were maintained during the tests with intake air temperatures ranging between 110 to 1500 Fahrenheit. The average valve recession wear rates of the lubricating compositions of Example 1 and Comparative Example A were calculated by a linear fit based on the last 300 hours of data from each test and reported on a wear rate per 1000 hours. The exhaust valve recession results are presented in Table 1. In this Table, the lower valve wear recession rate represents greater exhaust valve seat recession prevention efficacy.

TABLE 1 Waukesha F11 Exhaust Valve Recession Results Average Exhaust Valve Wear Sulfated Ash Recession Rate Ex./Comp. Ex. (wt. %) (in/1000 hr) 1 0.46 −0.00052 A 0.50 0.00071

As the data show, the lubricating oil composition of Example 1 exhibited superior prevention of exhaust valve wear recession over the lubricating oil composition of Comparative Example A containing a zinc dialkyldithiophosphate wear inhibitor.

It will be understood that various modifications may be made to the embodiments disclosed herein. Therefore the above description should not be construed as limiting, but merely as exemplifications of preferred embodiments. For example, the functions described above and implemented as the best mode for operating the present invention are for illustration purposes only. Other arrangements and methods may be implemented by those skilled in the art without departing from the scope and spirit of this invention. Moreover, those skilled in the art will envision other modifications within the scope and spirit of the claims appended hereto. 

1. A method for preventing or inhibiting exhaust valve seat recession in a natural gas fueled engine, the method comprising lubricating the engine with a lubricating oil composition comprising (a) a major amount of an oil of lubricating viscosity; and (b) a minor amount of a natural gas engine oil additive package comprising (i) one or more ashless dispersants, wherein the one or more ashless dispersants includes a bissuccinimide, (ii) a metal-containing detergent mixture comprising a first metal-containing detergent which is an overbased alkaline earth metal sulfonate or phenate detergent having a base number of about 100 to about 450 and a second metal-containing detergent which is an overbased alkaline earth metal sulfonate or phenate detergent having a base number of about 10 to about 50, and (iii) one or more antioxidants, wherein the lubricating oil composition is substantially free of each of any zinc compounds and alkaline earth metal salts of a condensation product of an alkylene polyamine, an aldehyde and a substituted phenol, and further wherein the lubricating oil composition has a sulfated ash content of about 0.1 wt. % to about 1.5 wt. % as determined by ASTM D
 874. 2. The method of claim 1, wherein the oil of lubricating viscosity is a natural gas engine lubricating oil. 3.-4. (canceled)
 5. The method of claim 1, wherein the bissuccinimide ashless dispersant is derived from one or more polyalkylene succinic anhydrides.
 6. The method of claim 5, wherein the polyalkylene group is a polyisobutenyl group having an average molecular weight of from about 700 to about
 2300. 7. The method of claim 1, wherein the one or more ashless dispersants is present in an amount of about 1 wt. % to about 8 wt. %, based on the total weight of the lubricating oil composition. 8.-10. (canceled)
 11. The method of claim 1, wherein the one or more metal-containing detergents is present in an amount of about 0.5 wt. % to about 8.5 wt. %, based on the total weight of the lubricating oil composition.
 12. The method of claim 1, wherein the first metal-containing detergent is present in an amount of about 0.5 wt. % to about 5 wt. % and the second metal-containing detergent is present in an amount of about 0.1 wt. % to about 1 wt. %, based on the total weight of the lubricating oil composition.
 13. The method of claim 1, wherein the one or more antioxidants is a hindered phenol compound.
 14. The method of claim 1, wherein the one or more antioxidants is present in an amount of about 0.1 wt. % to about 3 wt. %, based on the total weight of the lubricating oil composition.
 15. (canceled)
 16. The method of claim 1, wherein the lubricating oil composition has a sulfated ash content of about 0.15 to about 0.5 wt. % as determined by ASTM D
 874. 17. The method of claim 1, wherein the lubricating oil composition comprises: about 1 wt. % to about 8 wt. % of one or more ashless dispersants, about 0.5 wt. % to about 8.5 wt. % of one or more metal-containing detergents, and about 0.1 wt. % to about 3 wt. % of one or more antioxidants, based on the total weight of the lubricating oil composition.
 18. A natural gas engine lubricating oil composition comprising (a) a major amount of an oil of lubricating viscosity, (b) one or more ashless dispersants, wherein the one or more ashless dispersants includes a bissuccinimide, (c) a metal-containing detergent mixture comprising a first metal-containing detergent which is an overbased alkaline earth metal sulfonate or phenate detergent having a base number of about 100 to about 450 and a second metal-containing detergent which is an overbased alkaline earth metal sulfonate or phenate detergent having a base number of about 10 to about 50, and (d) one or more antioxidants, wherein the lubricating oil composition is substantially free of each of any zinc compounds and alkaline earth metal salts of a condensation product of an alkylene polyamine, an aldehyde and a substituted phenol, and further wherein the lubricating oil composition has a sulfated ash content of about 0.1 wt. % to about 1.5 wt. % as determined by ASTM D
 874. 19. The natural gas engine lubricating oil composition of claim 18, wherein the oil of lubricating viscosity is a natural gas engine lubricating oil.
 20. (canceled)
 21. The natural gas engine lubricating oil composition of claim 18, wherein the bissuccinimide ashless dispersant is derived from one or more polyalkylene succinic anhydrides.
 22. The natural gas engine lubricating oil composition of claim 21, wherein the polyalkylene group is a polyisobutenyl group having an average molecular weight of from about 700 to about
 2300. 23.-25. (canceled)
 26. The natural gas engine lubricating oil composition of claim 18, wherein the one or more antioxidants is a hindered phenol compound.
 27. (canceled)
 28. The natural gas engine lubricating oil composition of claim 18, having a sulfated ash content of about 0.15 to about 0.5 wt. % as determined by ASTM D
 874. 29. The natural gas engine lubricating oil composition of claim 18, comprising: about 1 wt. % to about 8 wt. % of one or more ashless dispersants, about 0.5 wt. % to about 8.5 wt. % of one or more metal-containing detergents, and about 0.1 wt. % to about 3 wt. % of one or more antioxidants, based on the total weight of the lubricating oil composition.
 30. The natural gas engine lubricating oil composition of claim 18, which has an exhaust valve seat recession reducing property greater than that of a corresponding natural gas engine lubricating oil composition in which a zinc compound is present therein.
 31. The method of claim 1, wherein the overbased alkaline earth metal sulfonate or phenate detergent having a base number of about 100 to about 450 is a sulfurized calcium phenate and the overbased alkaline earth metal sulfonate or phenate detergent having a base number of about 10 to about 50 is a calcium sulfonate.
 32. The natural gas engine lubricating oil composition of claim 18, wherein the overbased alkaline earth metal sulfonate or phenate detergent having a base number of about 100 to about 450 is a sulfurized calcium phenate and the overbased alkaline earth metal sulfonate or phenate detergent having a base number of about 10 to about 50 is a calcium sulfonate. 